Mixtures of phenyl-azo-phenyl dyestuffs

ABSTRACT

A mixture of dyestuffs of the general formulas (I) and (II),   wherein R and R&#39;&#39; are lower alkyl groups, W is a lower alkyl group and W&#39;&#39; is a phenol group is disclosed. The respective components of the mixture are contained in an amount of more than 20 percent by weight. The mixture of dyestuffs has a particularly superior dyeing affinity to a polyester fiber.

United States Patent [72] Inventors Nobujiro Ono Tokyo; l-liroshiHattorl, Yokohama; Shoji Tada,

Kasukabe-shi; Tsunetoshl Kaida, Tokyo, all

[54] MIXTURES 0F PHENYL-AZO-PHENYL DYESTUFFS 3 Claims, No Drawings [52]US. Cl 260/207, 8/26, 8/41 C, 260/562 K [51] Int. Cl C07c 107/06, C09b29/26 [50] Field of Search 260/207, 207.1

[56] References Cited UNITED STATES PATENTS 2,323,314 7/1943 Dickey eta1 260/207.1 X 3,478,011 11/1969 Artz 260/207.1 X

Primary ExaminerCharles B. Parker Assistant Examiner-Charles F. WarrenAttorney-Birch, Swindler, McKie & Beckett ABSTRACT: A mixture ofdyestuffs of the general formulas NHCOR' cHcmo-w' NHCOR I 1 wherein Rand R are lower alkyl groups, W is a lower alkyl group and W is a phenolgroup is disclosed. The respective components of the mixture arecontained in an amount of more than 20 percent by weight. The mixture ofdyestuffs has a particularly superior dyeing affinity to a polyesterfiber.

MIXTURES OF PHENYL-AZO-PHENYL DYESTUFFS NHCOR The present inventionrelates to a monoazo dyestuff and to a process for producing the same.The present invention also relates to a mixture of the monoazo dyestuffproduced in accordance with the process of the present invention.

The monoazo dyestufl' of the present invention is represented by thegeneral formula (I) X OR Z OzN- -N=N N Y i l CH2CHCH:QW

wherein X is a halogen, Y is a nitro or cyano group, R and R are loweralkyl groups, Z is a hydrogen or a lower alkyl group capable of having asubstituent, P is a hydrogen or a lower acyl group, Q is an oxygen or asulfur and W is an alkyl, aralkyl or aryl group.

It has been well known in the art that previous dyestuffs havedisadvantages in the point of dyeing affinity a hydrophobic fiber, inparticular to a polyester fiber, as well as in the point of light andheat resistances of dyeings therewith. And prominently the previousdyestuffs belonging to this monoazo system are liable to be afiected inthe dyeing affinity thereof with a pH of dye bath at the time of dyeing,that is to say, the dyeing affinities thereof are fluctuated largelydepending on variations of the pH of the same. Accordingly, in order 'toob-' tain a desirable dyeing density, it has been requested to carry outa strict regulation of the pH of dye bath.

One of ,the objects of the present invention'is to provide a:

monoazo dyestuff which has an excellent dyeing affirrity to a ahydrophobic fiber, in particular to a polyester fiber, together withsuperior light and heat resistances of dyeing therewith.

Another object of the present invention is to provide a mixture ofmonoazo dyestuffs produced in accordance with theprocess of the presentinvention, which has a particularly excellent dyeing affinity to apolyester fiber.

A further object of the present invention is to provide a composition ofmonoazo dyestuffs produced by the use of a mixture of couplingcomponents of two kinds or more in accordance with the process of thepresent invention, which has an especially superior dyeing affinity to apolyester fiber.

A furthermore object of the present invention is to provide a processfor producing the monoazo dyestufi by diazotizing an amine of thegeneral formula (ll) 02N- NH: (mi

and coupling the resultant diazotized solution to an amine of. thegeneral formula (III) wherein X, Y, R, R, Z, W, P and have the foregoingsig-, nificances.

A still further object of the present invention is to provide a, processfor producing the monoazo dyestuff by acylating a; dyestuff of thegeneral formula (IV) NllCOR wherein X. Y, R, R, Z, W and 0 have theaforedescribed significances.

These and other objects and advantages of the present invention willbecome apparent to those skilled in the art from a rnncirlnrarinn nf rhpnnrlermentinned snecification and claims.

In accordance with the present invention, it has been found that thepresent monoazo dyestuff has an excellent dyeing affinity to ahydrophobic fiber, in particular to a polyester fiber and the dyeingtherewith shows a remarkable fastness in respects to a light resistanceand a heat resistance, and further present dyestuff is scarcely affectedin the dyeing affinity thereof with variations of a pl-l of dye bath inthe course of dyeing operation, which leads to advantages of being usedeasily tor practical applications. In addition, it has also been foundthat, mixing two kinds or more of the present dyestuffs at an optionalratio or producing a dyestuff composition by the use of a mixture of twokinds or more of coupling components at an optional percentage in thecourse of coupling, there is obtained a dyestuff having a particularlysuperior dyeing affinity to the polyester fiber. Each components arepreferably contained in an amount of more than 20 percent.

The present dyestufi" is produced by diazotizing an amine of the generalformula (ll) mentioned below and then coupling the resultant diazotizedsolution to a coupling component of the general formula (III) describedhereunder, or, if desired, by treating a dyestuff of the general formula(IV) mentioned hereinafter with an acylation agent, in case where P is ahydrogen:

I OH

' wherein X, Y, R, R, Z, W, P and Q have the aforesaid significances.

cludes;

The amine represented by the general formula (ll) used for theproduction of the dyestuff of the present invention in-2-bromo-4,6-dinitroaniline, dinitroaniline,2-bromo-4-nitro-6-cyanoaniline, 2-chloro-4- nitro--cyanoaniline and thelike.

Further, the coupling component represented by the general formula (III)includes; 3-acetylamino-6-methoxy-N-(I-phenoxy-B-hydroxy-propyl)-aniline, 3-propyonylamino-6-methoxy-N-(F'butoxy-B-hydroxy-propyl)-aniline, 3acetylamino-6-methoxy-N-(I-phenoxy-B-acetoxy-propyl)- aniline,3-acetylamino-6-ethoxy'N-(cyanoethyl)-N-(lphenoxy/3-hydroxy-propyl)-aniline,3-propyonylamino-6- propyl]-aniline,3-acetylamino-6-methoxy-N-(I-benzylthio-B- hydroxy-propyl)-aniline andthe like. These components are synthesized by condensating4-acylamino-Z-amino-anisole, 4- acylamino-Z-ethylamino-anisole,4-acylamino-2-aminophenetole, 4-acylamino-2-cyanoethylamino-phenetole orthe like with an epichlorohydrin and then reacting the resultantcondensate with sodium alcoholate, sodium-alkyl mercaptide,

' phenol, and thiophenols, or by condensating the same withalkylglycidylether, arylglycidylether and alkyl-glycidyl thioether. Inaddition, if desired, these coupling components can be further acylatedin a freed hydroxyl group thereof by:-

treating with an acylation agent such as acetyl chloride, propyonylchloride and the like.

The amine represented by the general formula (ll) is easily diazotizedin an ordinary manner by effecting in a cone. sul- 2-chloro-4,6-

out rddiEtThE is's'iiy obtained the objective dyestuff represented bythe general formula (l). in the case where P is a hydrogen in thegeneral formula (III), dissolving the dried dyestuff in an inactiveorganic solvent such as acetone, dioxane and the like and reacting theresultant solution with an acetylation agent such as acetyl chloride,acetic anhydride, propyonyl chloride and the. like at a temperature inthe range of from to 65 C. in the presence of a neutralization agent foracid such as pyridine, anhydrous sodium acetate and the like, there iseasily carried out an acylation of a freed hydroxyl group therein.

in the course of dyeing a polyester fiber material by the use of thedyestuff in accordance with the present invention, it is of advantage toemploy the finely powdered dyestuff in a form of being dispersed in thedye bath. Accordingly, it is preferable to be employed in a form ofdispersoid which is prepared by being ground for a long time togetherwith a dispersing agent and wetting agent such as waste solution ofcellulose sulfite, condensate of alkylnaphthalene sulfate and formal--dehyde and the like. The dyeing is carried out at a temperature rangingfrom 95 to 105 C. in the presence of a carrier, while at 120 to 140 C.in the absence of the carrier. In case of textile printings, the dyeingis so performed as that a printed fabric material is treated with a dryheating at a comparatively higher temperature, for instance at about 200C., within a short time or is steamed under the increased pressure. As acarrier in this method, o-phenylphenol, salicylate ester, chlorobenzene,methylnaphthalene and the like can be employed. In order to improve arubbing resistance, it is preferable to effect an after-treatmentreductively over a dyed material of a printed material in a bathcontaining, for instance, sodium dithionate, sodium hydroxide anddetergent. The polyester fiber thus dyed or printed is uniform in dyeingand has a favorable light resistance and a prominent heat resistance.

The following examples are given merely as illustrative of the presentinvention and are not to be considered as limiting. Unless otherwisespecified, the parts therein are by weight.

EXAMPLE 1 1.5 parts of sodium nitrite are charged to 37 parts of cone.sulfuric acid at a temperature of C. or lower and dissolved therein byincreasing the temperature gradually and heating with stirring at 60+ C.for minutes. 5.3 parts (0.02 mole) of 2,4-dinitro-6-bromo-aniline arecharged thereto at room temperature and dissolved. By increasing thetemperature to 50 C. and stirring at said temperature for 2 hours, adiazotization of the resultant solution is completed.

On the other hand, to a mixed solution of 10 parts of acetic acid, 30parts of methanol, 40 parts of water and 10 parts of conc. hydrochloricacid containing 6.6 parts (0.02 mole) of 4-acetylamino-2-(F-phenoxy-fi-hydroxy-propylamino)-aniline is added 30parts of ice and maintained at 5 C. or lower. To this mixed solution isadded dropwise with stirring at 0 to 5 C. in the course of 1 hour theforegoing diazotized solution. After stirring at said temperature for afurther 1 hour, 30 parts of iced water are added thereto and a couplingis accomplished at 5 to 7 C. for an additional 1 hour with stirring.Filtering out and washing with water the separated-out product, thereare obtained 10.5 parts of dyestuff having the undermentioned structuralformula; I

OCHa

Oll NHCOCIla By the use of this dyestufi', there is obtained a polyesterfiber dyed to fast navy blue.

The foregoing coupling component is prepared as follows. That is to say,by heating with stirring for 4 hours under the refluent condition 3.6parts (0.02 mole) of 4-acetylamino-2- amino-anisole, 3.3 parts (0.022mole) of phenylglycidyl ether and 10 parts of methanol, a condensationis completed to produce 0.02 mole of4-acetylamino-(F-phenoxy-B-hydroxypropylamino)-anisole. To the productis added and dissolved at a temperature of 15 C. or lower a mixedsolution of 10 parts of conc. hydrochloric acid, 10 parts of aceticacid, 20 parts of methanol and 40 parts of water to prepare theaforestated coupling solution.

EXAMPLE 2 As described in example 1, a diazotized solution is producedby the use of 5.3 parts (0.02 mole) of 2,4-dinitro-6-bromoanisole. 0nthe other hand, to a mixed solution of 20 parts of methanol, 50 parts ofwater and 10 parts of conc. hydrochloric acid containing 5.3 parts (0.02mole) of 4-acetylamino-2-( lmethoxy-B-hydroxypropylamino)-anisole isadded 50 parts of ice and maintained at 5 C. or lower. To this mixedsolution is added dropwise with stirring at a temperature of 0 to 5 C.in the course of 1 hour the foregoing diazotized solution. Stirring iscontinued at said temperature for a further 1 hour, then 300 parts oficed water are added, 10 percent solution of soda ash is added furtheruntil a pH becomes to 4 to 5, and stirring is i still continued at 5 to10 C. for an additional 1 hour to accomplish a coupling. Filtering outand washing with water the j separated-0ut product, there are obtained6.8 parts of dyestuff having the undermentioned structural formula,

. refluent condition. A methoxyl substitution is thus completed toproduce 5.3 parts of the objective 4-acetylamino-2-(I-methoxy-B-hydroxypropylamino)'anisole. To this product is added at 15 C.a mixed solution of 10 parts of hydrochloric acid and 50 parts of waterto prepare the coupling solution.

EXAMPLE 3 As described in example I, a diazotized solution is producedby the use of 5.3 parts of 2,4-dinitro-6-bromo-aniline.

On the other hand, to a mixed solution of 10 parts of acetic acid, 30parts of methanol, 40 parts of water and 10 parts of hydrochloric acidcontaining 1.6 parts of4-acetylarnino-2-(fimethoxy-B-hydroxypropylamino)-anisole and 4.6 partsof 4- acetylamino-2-( F-phenoxy-B-hydroxypropylamino)-anisole is added30 parts of ice and maintained at 5 C. or lower. To this mixed solutionis added dropwise with stirring at a temperature of 0 to 5 C. in thecourse of 1 hour the above-mentioned diazotized solution. Stirring iscontinued at said temperature for a further 1 hour, then 300 parts oficed water are added and stirring is still continued at 5 to 7 C. for anadditional 1 hour to complete a coupling. Filtering out and washing withwater the separated-out product, there are obtained 10.2 parts EXAMPLE 4As mentioned in example 1, a diazotized solution is prepared by the useof 5.3 parts of 2.4-dinitro-6-bromoaniline.

On the other hand, to a mixed solution of 20 parts of methanol, 50 partsof water and 10 parts of conc. hydrochloric acid containing 6.3 parts(0.02 mole) of 4-acetylamino-2-[B-(fi-hydroxyethylthio)-/8-hydroxypropylamino]-anisole is added 50 pans ofice and maintained at 5 C. or lower. To this mixed solution is addeddropwise with stirring at a temperature of to C. in the course of 1 hourthe foregoing diazotized solution. Stirring is continued at saidtemperature for a further 1 hour, then 300 parts of iced water areadded, percent solution of soda ash is further added until a pH becomesto 4 to 5, and stirring is still continued at 5 to 10 C. for anadditional 1 hour to accomplish a coupling. Filtering out and washingwith water the separated-out product, there are obtained 7.] parts ofdyestuff having the structural formula mentioned hereinafter;

Br 0 CH: OzN- N=N-NHCH:CHCH2SC2H4OH (in N02 NHCOCHz By the use of thisdyestuff, there is obtained a polyester dyed to fast navy blue.

The foregoing coupler is prepared as follows. That is to say, by heatingwith stirring for 3 hours under the refluent condition 3.6 parts of4-acetylamino-Z-amino-anisole, 2.0 parts of epichlorohydrin and 20 partsof methanol, 4-acetylamino-2-(B -chloro-B-hydroxypropylamino)-anisole isprepared. To this product is added 3.0 parts of mercaptoethanol and 2.0parts of sodium bicarbonate to react for 6 hours under the refluentcondition. Thus 6.3 parts of the objective 4-acetylamino-2-[F-(,B-hydroxyethylthio)-es-hydroxypropylamino[-anisole are quantitivelyproduced. To this product is added at a temperature of C. or lower amixed solution of 10 parts of hydrochloric acid and 50 parts of water toprepare the coupling solution.

EXAMPLE 5 ponent the undermentioned structural formula;

5.4 parts of the dyestuff powders described in example 2 are added withstirring and dissolved into 50 parts of acetone. 2.5 parts of pyridineare added to the resultant solution, and then 1.7 parts of acetylchloride are added at 25 to 30 C. in the course of 30 minutes. Stirringis continued for 1 hour at that condition. 4.0 parts of anhydrous sodiumacetate are added and further 3.5 pans of acetyl chloride are addeddropwise at to 30 C. in the course of 1 hour. Stirrings are carried outat to C. for 1 hour, at to C. for another 1 hour and at to C. for anadditional 1 hour to accomplish an acetylation. By pouring theacetylated solution into 300 parts of water, the underdescribed dyestuffis separated out, which is filtered out and washed with water;

7 Thus there are obtained 5.5 parts of dyestuff with which a polyesterfiber is dyed to reddish navy blue.

EXAMPLE 7 1.5 parts of sodium nitrate are charged to 37 parts of conc.sulfuric acid at 10 C. or lower and dissolved therein by increasing thetei nperature gradually and heating with stirring at 60-:2 C. for 15minutes. 5.0 parts (0.02 mole) of 2,4-dinitro- -chloro-aniline arecharged thereto at room temperature and dissolved therein. Increasingthe temperature to 50 with stirring for 2 hours, there is completed adiazotization of the resultant solution.

On the other hand, to a mixed solution of 10 parts of acetic acid, 30parts of methanol, 40 parts of water and 10 parts of conc. hydrochloricacid containing 7.0 parts (0.02 mole) of 4-acetylamino-Z-[N-ethyl-N-(Ibutoxy-B-acetyloxypropyl)1- aminophenetole isadded 30 parts of ice and maintained at 5 C. or lower. To this mixedsolution is added dropwise with stirring at 0 to 5 C. in the course of 1hour the foregoing diazotized solution. Stirring is continued for afurther 1 hour, then 300 parts of iced water are added thereto and theresultant mixed solution is stirred for an additional 1 hour. Filteringout and washing with water the separated-out product, there are obtained7.5 parts of dyestuff having the undermentioned structural formula:

COCH:

I IHCOCH:

By the use of this dyestuff, there is obtained a polyester fiber dye tonavy blue.

The foregoing coupler is synthesized as mentioned below. That is to say,reacting for 3 hours at the refluent condition 4.4 parts of4-acetylamino-2-ethylamino-phenetole and 2.8 parts of butylglycidylother with 20 parts of methanol, there is produced 4-acetylamino-2-[N-ethyl-N-(F-butoxy-B-hydroxypropyl)]-aminophenetole. 50 parts of dioxaneare added thereto and the methane] is distilled out at 70 to C. Then 3parts of pyridine are added to the resultant solution and 20 parts ofacetyl chloride are added dropwise at 20 to 30 C. Stirring is continuedat said temperature for 3 hours to synthesize the coupler having as amain component the ob jective 4-acetylamino-2-[N-ethyl-N-(F-butoxy-fl-acetyloxypropyl) ]-aminophenetole.

EXAMPLE 8 As described in example 7, a diazotized solution is producedby the use of 5.0 parts of 2,4-dinitro-6-chloro-aniline.

On the other hand, to a mixed solution of 10 parts of acetic acid, 30parts of methanol, 40 parts of water and 10 parts of hydrochloric acidcontaining 7.8 parts of 4-acetylamino-2-[N-cyanoethyl-N-(F-phenoxy-fi-hydroxypropyl ]-amino-anisole is added 30parts of ice and maintained at 5 C. or lower. To this mixed solution isadded dropwise at 0 to 5 C. in the course of about 1 hour the foregoingdiazotized solution. Stirring is continued at a temperature of 5+ C. for1 hour, then 300 parts of iced water are added thereto and the resultantsolution is further stirred for an additionall hour. Filtering out andwashing with water the separated-out product, there are obtained 9.3parts of dyestuff having the underdescribed structural formula:

i 3.3 parts of phenyl glycidyl ether are added thereto and the resultantsolution is heated with stirring at 80+ C. for another hours to produce4-acetylamino-2-[N-cyanoethyl-N-(I-phenoxy-B-hydroxypropyl)]-amino-anisole. To said solution is addedand dissolved at 15 C. or lower a mixed solution of parts ofhydrochloric acid, 30 parts of methanol and 40 parts of water to preparethe coupling solution.

EXAMPLE 9 1.5 parts of sodium nitrate are charged to 37 parts of conc.sulfuric acid at 10 C. or lower and dissolved therein by increasing thetemperature gradually and heating with stirring at 60:2 C. for minutes.4.8 parts (0.02 mole) of 2-cyano-4- nitro-o-bromo-aniline are chargedthereto at room temperature and dissolved therein. Stirring of theresultant solution is effected at to C. for 9 hours to carry out adiazotization.

On the other hand, to a mixed solution of 10 parts of hydrochloric acid,38 parts of methanol, 40 parts of water and 10 parts of acetic acidcontaining 5.8 parts of 4-propyonylamino-2-(I-ethoxy-B-hydroxypropylamino)-anisole is added 30 parts of iceand maintained at 5 C. or lower. To said mixed solution is addeddropwise at 0 to 5 C. in the course of 1 hour the foregoing diazotizedsolution. After stirring of the resultant solution is effected at saidtemperature for another 1 hour, 300 parts of iced water are addedthereto and stirring is continued for an additional 1 hour while adding10 percent solution of sodium acetate until a pH becomes 5. Filteringout, washing with water and drying the separated-out product, there areobtained 8.2 parts of dyestuff having the structural formula mentionedbelow:

OCHz

NHCOCzH By the use of this dyestuff, there is obtained a polyester fiberdyed to blue.

The coupler is synthesized by employing the procedure of example 2 butreplacing 4-acetylamino-2-amino-anisole and sodium methylate with4-propyonyl-2-amino-anisole and sodium ethylate respectively.

EXAMPLE l0 l5 parts of sodium nitrate are added to 37 parts of cone.sulfuric acid at 10 C. or lower and dissolved therein by increasing thetemperature gradually and heating with stirring at 60fl C. for 15minutes. 3.9 parts of 2-cyano-4-nitro-6- chloro-aniline are addedthereto at room temperature and the resultant solution is stirred at 25to 30 C. for 3 hours, to carry out a diazotization.

On the other hand, to a mixed solution of 10 parts of hydrochloric acid,20 parts of acetone, 40 parts of water and 10 parts of acetic acidcontaining 7.5 parts of 4-acetylamino-2-(F-phenoxy-B-acetoxy-propylamino)-anisole is added 30 parts of ice andmaintained at 5 C. or lower. To the resultant mixed solution is addeddropwise with stirring at 0 to 5 C. in the course of about 1 hour theforegoing diazotized solution and stirring is further continued for anadditional 1 hour. 300 parts of iced water are added thereto andstirring is still further effected for another 1 hour. Filtering out andwashing with water the separated-out product, there are obtained 10.3parts of dyestufi having the structural formula described hereunder:

OCH;

By the use of this dyestuff, there is obtained a polyester fiber dyed toblue.

As mentioned in example 1, the coupler is synthesized by condensing at60 to 63 C. 4-acetylamino-2-amino-anisole and pheny glycidyl ether inacetone, adding pyridine thereto and then reacting the resultantsolution at room temperature with acetyl chloride.

DYElNG EXAMPLE 1 Thirty parts of the dyestuff described in example 1 areground for a long time with 65 parts of condensate comprisingalkylnaphthalene sulfonate and formaline as a dispersing agent, 5 partsof sodium polyalkyl naphthalene sulfonate as a wetting agent and someamounts of water, dried and pulverized. Dispersing 5 parts of theresultant dyestuff preparation into 2,000 parts of 1 g./l. solution ofsoapless soap, there is prepared a dye bath. One-hundred parts of apolyester fiber (Dacron) are impregnated in said dye bath and dyed atl30i2 C. for 1 hour under the increased pressure. The material is takenout from the dye bath and effected in a bath containing 2 g./l. ofsodium dithionate, 3 cc./l. of 34 Be sodium hydroxide and 1 g./l. ofnonionic detergent (polyglycol ether) at a temperature of to C. for 15minutes with a reductive after-treatment. Thus there is obtained a navyblue dyeing having an excellent heat resistance.

In the same manner as described above, employing dyestuffs mentioned inthe left column described hereinafter, there are obtained fast dyeingsof color phases described in the right column thereof:

Colour phase NHCOCH:

Colour phase Dyestulf of dyeing B1 CH3 02N--N=N- Nnomonoms-cliz Do.

I OH N 02 NHC O C2H5 Br 0 CH;

CZHICN OzN- N=N N\ D0.

CH CH-CHC4H0 N 0 NHC 0 OH;

B! 0 CH3 OzNC -N=N- NHCH2(IJ HOHzSCzHt-0H Blue.

OH ON NBC 0 OH:

BI O C 2H5 l CZHS OZN- N=N -N CHzOH-CHzO-CzHs C N NHO O CH;

9999 19.. CI 0 CH3 O2N N=N- NH0H2 JH-orns Do.

' 011 N NH0 0 CH3 DYEING EXAMPLE 2 to be regarded as a departitre fromthe spirit and scope of the d fd l b I present invention, and all suchmodifications are intended to Employing h proce 0 yemg examp l rep acmgbe included within the scope of the following claims. the dyestuff withparts of the dyestuff described in example It is claimed, thine obtaineda i preparation Dlspersm? 5 parts 1. A mixture of dyestuffs of thegeneral formulas (l) and of said dyestuff preparation mm 2,000 parts ofsolution com- (11) prising 0.5 g./l. soapless soap and 3 .g./l. sodiumof ortho-phenylphenol, there is prepared a dye bath. One-hundred partsof a polyester fiber (Dacron) are impregnated in said dye bath at 75 C.Then the dye bath is boiled during the lapse of 30 minutes therefrom.After boiling for 15 minutes, a small amount of 60 g./l. solution ofammonium phosphate is added and further 0.5 part of 10 percent aceticacid added thereto.

Thus dyed the material is dyed at the boiling for 90 minutes. Thematerial is taken out from the dye bath and rinsed reductively in thesame manner as described in the above dyeing example 1. Thus there isobtained a navy blue dyeing having an excellent heat resistance.

DYEING EXAMPLE 3 Employing the procedure of dyeing example 1 butreplacing the dyestuff with 30 parts of the dyestufi described inexample 9, there is obtained a dyestuff preparation. Twenty parts ofthis dyestuff preparation are added to 80 parts of an original printingsolution having an undermentioned composition and dispersed qisat ihy ma f e his znaa itetsr;

COMPOSITION OF ORIGINAL PRINTING SOLUTION Total I00 parts A fabric ofpolyester (Dacron) is printed with this pastelike preparation, semidriedand then steamed for minutes under the gauge pressure of 3 to 4 kg./cmSubsequently, the fabric is rinsed with cold water for 10 minutes,squeezed and dried.

Thus

there is obtained a fast blue printed fabric.

The invention being thus described, it will be obvious that the same maybe varied in many ways. Such variations are not I Br OzN- N=N-NrwmcHcrno-O 5 Br 0 R wherein R and R are lower alkyl groups, W is alower alkyl group CHzCHCHzO-W CHzCHCHzO-W' N0 NHCOR and W is a phenylgroup, the respective components of said mixture being contained in anamount of more than 20 percent by weight.

2. A mixture of dyestuffs of the structural formulas (A) and O C B3NHCOCHa Br 0 CH3 (B) O2N-- N=N NHCHztEHCHz-O OH;

I OH NO: 5 529921 the res pective components of said mixture beingcontained in

2. A mixture of dyestuffs of the structural formulas (A) and (B),
 3. Themixture of claim 2 wherein the weight ratio of dyestuff (A) to dyestuff(B) is about 7:3.